|Publication number||US5780155 A|
|Application number||US 08/798,370|
|Publication date||Jul 14, 1998|
|Filing date||Feb 10, 1997|
|Priority date||Aug 11, 1994|
|Publication number||08798370, 798370, US 5780155 A, US 5780155A, US-A-5780155, US5780155 A, US5780155A|
|Inventors||Sei Ishizawa, Masayasu Suzuki, Hirokazu Terada|
|Original Assignee||Chisso Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (11), Classifications (12), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation-in-part of application Ser. No. 08/501,309 filed on Jul. 12, 1995, now abandoned.
1. Field of the Invention
The present invention relates to melt-adhesive composite fibers and a process for producing the composite fibers. Further, the present invention relates to a partially fused fabric comprising the composite fibers and having a high strength, high bulk recovery from compression, excellent formation characteristics of few neps (small fiber aggregates), and soft hand feeling. Still further, the present invention relates to a surface material, for medical supplies such sanitary napkins and paper diapers, comprising the partially fused fabric.
2. Description of Related Art
In recent years, the performances required to non-woven fabrics used for surface materials for medical supplies such as sanitary napkins and paper diapers have been advanced and diversified; and specifically such non-woven fabrics have been required that the fabrics maintain a high strength at a basis weight as small as possible, have a high bulk recovery from compression, have limited number of naps (small fiber aggregates) as a formation characteristic of fabric, and have a soft hand feeling.
In order to satisfy these requirements, a process for producing a bulky non-woven fabric has been proposed in Examined Japanese Patent Publication No. 1-37505 wherein melt-adhesive composite fibers are partially fused, in the production of which fibers the Q value of the first component, preheating temperature, stretching ratio, number of crimps, and crimp elasticity are specified.
However, the non-woven fabric is still unsatisfactory as a surface material for medical supplies, and specifically the non-woven fabric obtained in the Publication '505 had the problems that troubles occur at the carding step; many neps are formed to deteriorate the fabric performances; bulk recovery is low; strength is low, and hand feeling is poor. Thus, the development of a non-oven fabric which solves such problems as mentioned above has strongly been desired.
3. Summary of the Invention
As a result of diligent research on the performances of non-woven fabrics comprising melt-adhesive composite fibers and processes for producing such fabrics, it has been fund that the defects in the prior art have been solved by the present invention as follows:
The present invention is to provide melt-adhesive composite fibers comprising a first component comprising a crystalline polypropylene and a second component comprising mainly a polyethylene, the components being arranged in a side-by-side or sheath-core relationship wherein the second component is continuously present on at least a part of the fiber surface in the lengthwise direction of the fiber, having three-dimensional crimps of 4 to 16/inch, having a filamentary denier of 1.0 to 2.0, and having an apparent length of 20 to 40 mm.
The composite fibers of the present invention can be produced by conducting
a step of spinning the polymer components by using a spinneret for a side-by-side or sheath-core type composite fiber,
a step of stretching unstretched filaments thus obtained at a temperature of higher than 90° C., but lower than 130° C. at a stretching ratio of 0.60 to 0.85 time the maximum stretching ratio,
a step of cooling the stretched filaments to a temperature lower than a preheating temperature and subjecting the filaments to a crimping treatment, and
a step of subjecting the filaments to an annealing at a temperature of higher than 80° C., but lower than 120° C.
Further, the present invention is to provide a partially fused fabric comprising more than 50 % by weight of the melt-adhesive composite fibers mentioned above or the fibers obtained by the process according to the process mentioned above. In the fabric of the present invention, intersectional points of the composite fibers are melted to join with each other through the second component in the composite fibers.
Still further, the present invention is to provide a surface material, for medical supplies, having a thickness of greater than 1 mm, and comprising the partially fused fabric mentioned above.
FIG. 1 shows a cross-section of a composite fiber of the present invention.
The crystalline polypropylene used as a first component in the composite fibers of the present invention generally means a crystalline polymer containing polymerized propylene as a main component, and includes not only homopolymers of propylene but also copolymers of propylene with ethylene, butene-1, or 4-methyl pentene.
The polyethylene used mainly as a second component in the composite fibers of the present invention generally means a polymer such as a medium or low pressure polyethlyene and high pressure polyethylene containing polymerized ethylene as main component, and includes not only homopolymers of ethylene but also copolymers with propylene, butene-1, or vinyl acetate (EVA). The melting point of the polyethylene is preferably lower than the melting point of the crystalline polypropylene as the first component by 20° C. or more.
The crystalline polypropylene and polyethylene mentioned above may contain various additives, generally used for polyolefin fibers, such as a stabilizer, filler, and pigment within a range wherein the object of the present invention is not failed to achieve.
The melt-adhesive composite fibers in the present invention are ones extruded from a spinneret for side-by-side type or sheath-core type composite fiber. The second component is necessary to be continuously present on at least a part of the fiber surface in the lengthwise direction of the fiber, and the second component preferably occupy the fiber surface as broadly as possible. Since the melt-adhesive composite fibers develop crimps by utilizing the difference in the elastic shrinkage of the two components, an eccentric sheath-core structure as shown in FIG. 1 is preferable in the case where the composite fibers have a sheath-core type structure, and the center of the core component is preferably biased by 5 to 15% (based on the diameter of the sheath-core composite fiber) from the center of sheath component.
The composite fibers of the present invention can be obtained by conventional methods for spinning a side-by-side composite fiber or sheath-core composite fiber wherein the second component is used as sheath component. There is not any specific restriction on the ratio of the two components in the composite fiber, but the second component is preferably 40 to 70 % by weight.
The melt-adhesive composite fibers of the present invention are self-crimping composite fibers having crimps of helical form. The shape of crimps of the side-by-side or sheath core bicomponent (composite) fiber of the present invention is inherently helical in view of the fact that the crimps are developed as a result of the difference of shrinkage between the components in the bicomponent fiber. Helical crimps can be distinguished from zig-zag crimps in that the latter type are produced mechanically by passing fibers through a stuffer-box crimper under a high mechanical pressure. Fibers having helical crimps possess higher bulkiness and higher recovery from compression than those of the zig-zag type. The composite fibers preferably do not develop crimps at the time of a heat treatment for preparing a non-woven fabric, in other words, the composite fibers of the present invention preferably do not have latent crimps. When the fibers do not substantially have latent crimps at the heat treatment, the shrinkage of the fibers caused by the developments of crimps at the time of the heat treatment for preparing the non-woven fabric can be avoided.
The number of crimps of the melt-adhesive composite fibers in the present invention is generally 4 to 16/inch, and preferably 6 to 14/inch. When the number of crimps is less than 4/inch, it causes winding of fibers on a cylinder of a carding machine. When the number of crimps exceeds 16/inch, the opening becomes inferior, and results in the formation of neps at the time of non-woven fabric preparation.
The melt-adhesive composite fibers of the present invention are necessary to have a filamentary denier of 1.0 to 2.0. When the denier is less than 1.0, crimps become too fine and causes the formation of naps. When the denier exceeds 2.0, there is a tendency that the hand feeling becomes hard and the bulk recovery of the non-woven fabric from compression decreases.
The apparent cut length of the melt-adhesive composite fibers of the present invention is generally 20 to 40 mm, and preferably 25 to 35 mm, which corresponds to the cut length of 28 to 80 mm, preferably 35 to 60 mm. When the apparent cut length is less than 20 mm, the transfer property of the fibers in carding machines is inferior and it becomes a cause of troubles that the fibers wind around workers. When it exceeds 40 mm, entanglement of the fibers becomes noticeable and becomes a cause of nap formation.
The melt-adhesive composite fibers of the present invention have preferably the ratio of apparent cut length to cut length of 0.5 to 0.7. When the ratio is less than 0.5, the transfer property of the fibers in carding machines is inferior, and the fibers wind around cylinders, resulting in a cause of nap formation. When the ratio exceeds 0.7, entanglement of the fibers becomes too strong, winding of fibers on a taker-in roll is caused, and the carding step itself become impossible.
The method for producing the melt-adhesive composite fibers of the present invention comprises
a step of spinning the polymer components through a spinneret for side-by-side or sheath-core type composite fibers,
a step of stretching unstretched filaments thus obtained at a temperature of higher than 90° C., but lower than 130° C. at a stretching ratio of 0.60 to 0.85 time the maximum stretching ratio,
a step of cooling the stretched filaments to a temperature lower than a preheating temperature and subjecting to a crimping treatment, and
a step of subjecting the fiber to an annealing at a temperature of higher than 80° C., but lower than 120° C.
In the spinning step, the first component comprising a crystalline polypropylene and the second component comprising mainly a polyethylene are extruded through a spinneret for side-by-side or sheath-core type composite fibers to form filaments such that the second component continuously present on at least a part of the fiber surface.
In the stretching step, unstretched filaments as extruded are subjected to a preheating to a stretching temperature. When stretching temperature is lower than 90° C., crimps become too fine. When the stretching temperature exceeds 130° C., remarkable fusion of the composite fibers with each other unfavorably occur through the polyethylene.
When the stretching ratio is less than 0.60 time the maximum stretching ratio, the difference in elastic recovery of the two components become small and thus crimps are not developed. When the stretching ratio exceeds 0.85 time the maximum stretching ratio, the difference in elastic recovery of the two components become too large and the cycle of crimps become small. As the result, not only the number of crimps become too many and the apparent cut length of the fibers unfavorably become too short. The maximum stretching ratio means the stretching ratio at which fluffs begin to occur in filaments tow when the stretching ratio was gradually increased.
In the crimping treatment, stretched filaments are cooled at a temperature lower than the stretching temperature, the filaments are taken up with a roll such as a take-up roll of a nip roll under a tensioned condition, and then the filaments are relaxed to develop crimps. When the crimping treatment is carried out at a temperature exceeding the stretching temperature, development of crimps become insufficient.
In the annealing step, the filaments which developed crimps at the crimping treatment are subjected to an annealing at a temperature higher than 80° C., but lower than 120° C. for 0.5 to 30 min. When the annealing temperature is lower than 80° C., there is a fear that latent crimps are unfavorably developed at the step for preparing a non-woven fabric. When the annealing temperature is higher than 120° C., the crimps which were developed due to the difference in elastic recovery of the two components are extended and an apparent cut length of the fibers becomes unfavorably long.
The melt-adhesive composite fibers of the present invention are frequently cut to a predetermined length and used as staple fibers, and subjected to a card processing from the viewpoint of the easiness of processing to non-woven fabrics for a surface material for medical or sanitary supplies.
The partially fused fabric of the present invention may comprise more than 50% by weight, and up to 100% by weight of the melt-adhesive composite fibers mentioned above. The partially fused non-woven fabric can be obtained by converting the melt-adhesive composite fibers into a non-woven fabric by a conventional carding method, air-laid method, or dry-pulp method and then subjecting the non-woven fabric to a heat treatment to partially fuse the fabric. The partially fused non-woven fabric may comprise up to 50% by weight of polyester, polyamide, polypropylene, polyethylene, or other synthetic fibers, natural fibers such as cotton and wool, or regenerated fibers such as viscose rayon, as the fibers other than the melt-adhesive composite fibers. At this stage, the melt-adhesive composite fibers are necessary to be blended in an amount of 50% by weight or more in the fabric. When the content of the melt-adhesive composite fibers is less than 50% by weight, not only a fabric having a high non-woven strength can not be obtained since the fabric has few intersection of the fibers, but also a high bulkiness and a high bulk recovery of the fabric from compression as intended can not be obtained.
As the method for partially fusing the melt-adhesive composite fibers, a method by using a heated air dryer or suction band dryer can be exemplified. By applying these methods to the fabric, the intersections of the composite fibers are fused with each other through the melt of the second component to form a fabric. The temperature for the fusing is generally higher than the melting point of the second component, but lower than the melting point of the first component, and preferably 120° to 155° C. The time for the fusing is generally longer than 5 seconds when a dryer is used as an example.
The surface material for medical supplies of the present invention is one prepared by using the partially fused non-woven fabric, and usually has a thickness of greater than 1 mm. The surface material is desirable when the bulk characteristic is greater than 1 mm and elastic recovery from compression is higher than 50% in particular. When the thickness is less than 1 mm and the recovery is lower than 50%, a soft hand feeling of the material can not be obtained.
The thickness referred in this specification means the thickness (mm) which is determined by applying a load of 50 gf/cm2 on the material for 24 hours, allowing the material to stand under no load for 1 hour to recover the thickness, and then measuring the thickness (mm) under a load of 2 gf/cm2. The elastic recovery from compression means the difference designated as percentage (%) in the thickness of a surface material measured after a load of 50 kgf/cm2 was applied for 24 hours and the thickness of the same surface material measured after the material was left to stand under no load for 1 hour to recover its thickness.
According to the present invention, melt-adhesive composite fibers can be produced, which have a high bulk recovery, good formation characteristics, high strength, and soft hand feeling at the same time, and thus are useful as a surface material for medical supplies. Specifically, the partially fused fabrics of the present invention can be widely used for sanitary napkins and paper diapers.
The present invention will be described in more specifically with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. The values of physical properties in the Examples were determined by the methods as follows:
Number of crimps: The number of crimps of the melt-adhesive composite fibers was determined according to JIS L1015 (Test method for chemical fiber staples) 7.12.1.
Filamentary denier: The filamentary denier of the melt-adhesive composite fibers was determined according to JIS L1015 (Test method for chemical fiber staples) 7.5.1-A. The cut length of crimped fiber was determined by measuring the fiber length (mm) under a condition wherein the fiber was extended by applying the amount of load necessary to remove the crimps. The average value of 30 times of measurements was obtained.
Apparent cut length: The apparent cut length of the melt-adhesive composite fibers was determined by measuring the fiber length (mm) under no tension without extending the crimps of the staples and without applying an extra force to the staples. The average value of 30 times of measurements was obtained.
Bulk recovery: The bulk recovery of the partially fused non-woven fabric was determined by measuring the thickness (A) of a sample fabric after a load of 50 gf/cm2 was applied for 24 hours on the fabric, allowing the fabric to stand for 1 hour under no load to recover its bulk, measuring the thickness (B) of the fabric under a load of 2 gf/cm2, and calculating the bulk recovery according to the following equation: ##EQU1##
In evaluating the results, the fabrics having a bulk recovery of 50% or higher were regarded as acceptable and other fabrics were regarded as unaccetptable. Acceptable fabrics were designated as A and unacceptable fabrics were designated as C.
Strength of non-woven fabric: The strength of partially fused non-woven fabrics was determined according to JIS L1085 (Test for interlining cloth of non-woven fabric) in which a sample fabric of 5 cm wide was subjected to measuring for strength in the fabric direction (MD) and the direction perpendicular to the fabric direction (CD) by stretching the fabric under the conditions of a grip distance of 10 cm and a stretch rate of 30±2 cm/min. In evaluating the results, the fabrics having a MD strength of 2500 g/5 cm or higher were regarded as acceptable and lower than 2500 g/5 cm as unacceptable; and the fabrics having a CD strength of 500 g/5 cm or higher were regarded as acceptable and lower than 500 g/5 cm as unacceptable. Acceptable fabrics were designated as A and unacceptable fabrics were designated as C.
Number of naps: The number of naps of the partially fused non-woven fabrics was determined by counting the number of naps in 1 m2 of a sample fabric, and designated as the number/m2. In the evaluation, partially fused non-woven fabrics having one nap or less were regarded as acceptable and two or more as unacceptable. Acceptable fabrics were designated as A and unacceptable fabrics were designated as C.
Hand feeling: The hand feeling of the partially fused non-woven fabrics was determined by conducting sensory tests by 5 panelists. When all panelists judged a sample fabric as soft, the fabric was regarded as "excellent"; when 3 or more panelists judged a sample fabric as soft, the fabric was regarded as "good"; and when 3 or more panelists judged a sample fabric as insufficient in soft feeling, the fabric was regarded as "poor". Excellent fabrics were designated as A, good fabrics were designated as B, and poor ones were as C.
Fabric shrinkage: The shrinkage of the partially fused non-woven fabrics was determined by cutting a sample fabric into a size of 25 cm square, heating the fabric at 145° C. for 5 min -under no load with a dryer, measuring the shrinkage in the fabric direction at three points, and obtain the average value by calculation. In the evaluation, the fabrics having a shrinkage of lower than 10% were regarded as acceptable and the fabrics having a shrinkage of 10% or higher were regarded as unacceptable. Acceptable fabrics were designated as A and unacceptable fabrics were designated as C.
Each of the melt-adhesive composite fiber staples shown in Table 1 was obtained by extruding a polypropylene as the first component and a polyethylene as the second component through a spinneret having 350 orifices of a diameter of 0.6 mm for sheath-core or side-by-side type composite fiber to form filaments, stretching the filaments under the conditions shown in Table 1, and then cutting the stretched filaments into staples. The physical properties of the fibers thus obtained are shown in Table 1.
The staples of each of the melt-adhesive composite fibers thus obtained were formed into a web having a basis weight of 20 to 30 g/m2 by means of a carding machine, and the web was subjected to a heat treatment at a predetermined temperature of 135° to 140° C. for 5 sec with a suction band dryer to obtain a non-woven fabric in which intersections of the fibers were fused each other. The characteristics of the fabrics are shown in Table 2. In the Example 4 and Comparative Example 9 in Table 2, the staples in Example 1 and Comparative Example 3 were used.
TABLE 1__________________________________________________________________________Physical properties of melt-adhesive composite fibers__________________________________________________________________________ Composite First ratio Stretching Cooling Annealing compo- Second Composite 1st/2nd tempera- tempera- tempera- nent component structure components ture °C. ture °C. ture °C.__________________________________________________________________________Ex. 1 pp2) PE3) Sheath-core 50/50 115 50 100Comp. Ex. 1 " " " " " " 130Comp. Ex. 2 " " " " " " 100Comp. Ex. 3 " " " " " " "Comp. Ex. 4 " " " " 110 80 80Comp. Ex. 5 " " " " " " "Comp. Ex. 6 " " " " 115 50 100Ex. 2 " LL4) " 40/60 95 40 80Comp. Ex. 7 " " " " " " "Ex. 3 " PE3) Side-by side 50/50 110 100 100Comp. Ex. 8 " " " " " 60 60__________________________________________________________________________ Actual Maximum Number of Fila- Cut Apparent stretching stretching MS crimps/ mentary length cut ratio ratio ratio1) inch Crimp form denier mm length mm__________________________________________________________________________Ex. 1 4.0 4.8 0.83 11.3 Three- 1.5 51 34 dimensionalComp. Ex. 1 " " " 3.5 Three- " " 43 dimensionalComp. Ex. 2 4.4 " 0.92 18.2 Three- " " 21 dimensionalComp. Ex. 3 4.0 " 0.83 12.7 Machine5) " " 29Comp. Ex. 4 3.2 3.5 0.91 16.0 Three- 0.8 " 22 dimensionalComp. Ex. 5 2.0 " 0.57 3.1 Three- 1.5 " 43 dimensionalComp. Ex. 6 4.0 4.8 0.83 11.3 Three- " 64 44 dimensionalEx. 2 " 5.1 0.78 13.3 Three- 2.0 51 28 dimensionalComp. Ex. 7 3.3 " 0.64 13.9 Three- 3.0 " 25 dimensionalEx. 3 3.4 3.9 0.87 6.5 Three- 1.0 38 26 dimensionalComp. Ex. 8 " 3.8 0.89 15.1 Three- " " 17 dimensional__________________________________________________________________________ 1) MS ratio: Actual stretching ratio + maximum stretching ratio 2) PP: Crystalline polypropylene 3) PE: High density polyethylene 4) LL: Linear low density polyethylene 5) Machine: Crimp form obtained using a stuffing box
TABLE 2__________________________________________________________________________Physical properties of fused non-woven fabrics__________________________________________________________________________ Basis BulkinessContent weight Thickness Bulk recovery Strength characteristics % g/m2 mm % Evaluation MD g/5 cm Evaluation__________________________________________________________________________Ex. 1 100 25 2.0 61 A 2840 AComp. Ex. 1 Fibers of Comp. Ex. 1 were unable to form into a non-woven fabric.Comp. Ex. 2 100 25 1.9 68 A 2520 AComp. Ex. 3 " " 0.7 38 C 3150 AComp. Ex. 4 " " 1.7 57 A 2720 AComp. Ex. 5 Fibers of Comp. Ex. 5 were unable to form into a non-woven fabric.Comp. Ex. 6 100 25 1.6 60 A 2670 AEx. 2 " 30 2.2 53 A 3200 AComp. Ex. 7 " " 1.4 32 C 2200 CEx. 3 " 20 1.3 55 A 2610 AComp. Ex. 8 " " 1.0 62 A 2550 AEx. 4 506) 25 1.3 51 A 2950 AComp. Ex. 9 307) " 1.0 45 C 3030 A__________________________________________________________________________ Formation characteristics HandStrength characteristics Naps Fabric shrinkage feel- CD g/5 cm Evaluation number/m2 Evaluation % Evaluation ing__________________________________________________________________________Ex. 1 610 A 0 A 3.1 A AComp. Ex. 1 Fibers of Comp. Ex. 1 were unable to form into a non-woven fabric.Comp. Ex. 2 590 A 13 C 4.7 A BComp. Ex. 3 780 A 0 A 2.9 A CComp. Ex. 4 510 A 38 C 6.3 A BComp. Ex. 5 Fibers of Comp. Ex. 5 were unable to form into a non-woven fabric.Comp. Ex. 6 500 A 9 C 3.2 A BEx. 2 630 A 1 A 2.0 A AComp. Ex. 7 450 C 0 A 1.8 A CEx. 3 550 A 0 A 2.9 A AComp. Ex. 8 540 A 57 C 13.1 C BEx. 4 640 A 0 A 2.8 A AComp. Ex. 9 660 A 0 A 2.8 A B__________________________________________________________________________ 6) Fibers of Example 1 (50%) were blended with fibers of Comp. Ex. 3 (50%). 7) Fibers of Example 1 (30%) were blended with fibers of Comp. Ex. 3 (70%).
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4189338 *||Jul 29, 1975||Feb 19, 1980||Chisso Corporation||Method of forming autogenously bonded non-woven fabric comprising bi-component fibers|
|US5277974 *||Mar 1, 1993||Jan 11, 1994||Unitaka Ltd.||Heat-bondable filament and nonwoven fabric made of said filament|
|US5456982 *||Mar 29, 1993||Oct 10, 1995||Danaklon A/S||Bicomponent synthesis fibre and process for producing same|
|JPH0192416A *||Title not available|
|JPH01266216A *||Title not available|
|JPH03137223A *||Title not available|
|JPS4975869A *||Title not available|
|JPS6437505A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6001752 *||Mar 11, 1998||Dec 14, 1999||Chisso Corporation||Melt-adhesive composite fibers, process for producing the same, and fused fabric or surface material obtained therefrom|
|US6274237 *||May 19, 2000||Aug 14, 2001||Chisso Corporation||Potentially crimpable composite fiber and a non-woven fabric using the same|
|US6327736 *||Apr 1, 1999||Dec 11, 2001||Braun Gmbh||Bristle for a toothbrush|
|US6387488 *||Dec 15, 1998||May 14, 2002||Nissan Motor Co., Ltd.||Color-developing composite short fibers and color-developing structures employing the same|
|US6497458||Sep 10, 2001||Dec 24, 2002||Braun Gmbh||Bristle for a toothbrush|
|US6878650||Dec 20, 2000||Apr 12, 2005||Kimberly-Clark Worldwide, Inc.||Fine denier multicomponent fibers|
|US7378148 *||Nov 3, 2005||May 27, 2008||Motech Gmbh Technology & Systems||Multi-layer monofilament and process for manufacturing a multi-layer monofilament|
|US7674524||Feb 2, 2007||Mar 9, 2010||Teijin Fibers Limited||Thermoadhesive conjugate fiber and manufacturing method of the same|
|US7732357||Sep 14, 2001||Jun 8, 2010||Ahlstrom Nonwovens Llc||Disposable nonwoven wiping fabric and method of production|
|US7888275||Jan 17, 2006||Feb 15, 2011||Filtrona Porous Technologies Corp.||Porous composite materials comprising a plurality of bonded fiber component structures|
|US7968481 *||Dec 19, 2003||Jun 28, 2011||Kao Corporation||Hot-melt conjugate fiber|
|U.S. Classification||428/370, 428/374, 428/373|
|International Classification||D04H1/54, D04H1/42|
|Cooperative Classification||Y10T428/2931, Y10T428/2924, D04H1/42, Y10T428/2929, D04H1/5405|
|European Classification||D04H1/42, D04H1/54B|
|Dec 27, 2001||FPAY||Fee payment|
Year of fee payment: 4
|Jan 6, 2006||FPAY||Fee payment|
Year of fee payment: 8
|Dec 16, 2009||FPAY||Fee payment|
Year of fee payment: 12
|Apr 27, 2011||AS||Assignment|
Owner name: JNC CORPORATION, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHISSO CORPORATION;REEL/FRAME:026187/0940
Effective date: 20110412